The flavoring of vinegars with aromatic fruits and medicinal herbs is a practice with increasing trend mostly in countries with oenological tradition, resulting in a product of improved quality and consumer attractiveness. This study was directed towards the evaluation of the impact of the maceration process on the volatile signature of wine-based aromatic vinegars (WBAVs). The evaluation was performed using solid phase microextraction (SPME) combined with gas chromatography combined with mass spectrometry (GC-MS). Experimental parameters influencing headspace solid (HS)-SPME extraction efficiency, were optimized using an univariate experimental design. The best results were achieved using a polydimethylsiloxane (PDMS) fiber, 10 mL of vinegar sample, at 50 °C for 30 min of extraction. This way One hundred and three volatile organic compounds (VOCs), belonging to different chemical families including ethyl esters (37), higher alcohols (20), fatty acids (10), terpenoids (23), carbonyl compounds (six), lactones (five) and volatile phenols (two), were identified in wine vinegar (control) and WBAV. As far as we know, 34 of these VOCs are reported for the first time in macerated vinegars. Higher alcohols and lactones are the major chemical families in WBAV macerated with apple, whereas terpenoids are predominant in WBAV macerated with banana. The obtained data represent a suitable tool to guarantee the authenticity and genuineness of WBAV, as well as to promote the production of WBAV with improved sensorial and organoleptic properties. To the best of our knowledge, there are no reported studies dealing with the volatile signature of WBAV enriched with banana, passion fruit, apple and pennyroyal.